Jaroslav frohlich



Patented June 30, 1925.

UNITED srrrrizs IPA-TENT: OFFICE.

INDUSTRY m BASLE,. or BASEL, SWITZERLAND.

'rmw n'YEsTUrFs AND P OCESS or MAKING'SAME. I

No Drawing.

To all whom itmaly concern: I .Be it known that I, J AIRIOSILAVFRoHLrorr,

- a' citizen ofthe' Swiss Confederation, and residing at Basel,Switzerland, have in-' vented useful New Dyestuli's and Processes ofMaking' Same, of which the following is a full, clear, andiexactspecification.

.The present invention relates to ne'w'va-t 'dyestufif's which areparticularly, valuable .for producing fasttints on the animal fibre. Theinvention comprises the new dyestuifs',

. the method of making-same, and the material, dyed with the new vatdyestuffs. I

It has been found that valuable vat dye- 1 Ystufls are obtained bycausing a thionyl- 1' halide (SOHlg to act upon,2: 5 -diarylidoubenzoquinones'." Thisreaction may be condu cted inpresence'offa diluentand with ad} dition of an agent whichibinds acids, as foride,-andfacondensing agent, as i'forv example sulphui icjacid. Thetemperature and the proportionygwhich the. reacting substances bear toleach other may be varied within wide limits. I

J For obtaining dyestuffs of adarker tone it is ingenerall'jadvantageous to operate at higher temperatureswhich may riseto the boiling'point '.of; the diluent, as forinstance nitrobenzene.

Particularly suitable for the reaction are 2: 5-diarylidobenzoquinones,which i are not substituted orare only'mono-substituted (in 3-or6-position) the quinone nucleus. They react even 'at Iordinarytemperature with dyestufi formation, whereas the 3:6-disubstitution-derivatives inmost cases re- 'quire a higher;temperature. The 2:5-

diarylidobenzoquinones, the manufacture of 9 which is generally known,may be derived from two aromatic amines which may be the same ordifferent and may be mono-substituted at the nitrogen or monoorpolysubstituted at any position in the nucleus.

. As substituents there may be named, amon others, halo en, alkyl-,alkoxyl- (OCH phenyloxy- OC H n'itro-, amino-, alkylamino-,aralkylaminm, phenylamino-, hydroxylor carboxyl-groups.

The dyestuffs thus obtained form yellow to dark brown and black powdersand may contain halogen and sulphur. They dissolve in concentratedsulphuric acid to brown to red and blue solutions. With hydrosulphiteand caustic soda lye they give are suspended i example sodium acetate ormagnesium 'oxf I I I I at a somewhat higher temperature, for ex-Application fi ed c bpb er as, 1924. I ser ai Ymfmeam.

I bright yellow 'to brown vats from which.

woolis dyed fast yellow to brown, olive and grey tints.

The following'examples illustrate the invention without, however,limiting the scope c "parts of nitrobenzene, 9 parts of thionyl addedand the whole stirred for several hours at below 5 C.

A test sample is filtered .and the solid matter washed; it is agreenish-yellow powder which dissolves in concentrated sulphuric acid toa redsolution and dyes wool in a hydrosulphite vat a purer yellow thanthat of the parent dyestufl".

If the mixture is stifijred for a long time ample at 15 (1, there isobtained by filtering and washing a bright brown powder chloride (S001are of the same, the parts .being I by weight Q Example-1. parts of 5dianilidobenzoquinone Y I These products contain chlorine and alsosulphur.

I Example 2.

40 parts of 2:5 dianilido-6-chloro lz4- benzoquinone are suspended in800 parts of nitrobenzene and the suspension is mixed at 5 C. with 40parts of thionyl chloride. The whole is stirred for a longtime in thecold or at ordinary temperature and there is obtained a dyestuff whichis a bright brown powder, soluble in concentrated sulphuric acid to ared violet solution and dyeing wool in the vat yellow-brown tints. Asimilar dyestufi' isobtained by operating without a diluent. By raisingthe temperature the tint of the dyestuff is shifted towards red. Forexample, if the temperature of the operation is -120 C. and continuedfor some time, there is obtained a dyestuif which dissolves .insulphuric acid to a violet solution and dyes wool in the vatorange-brown; if the temperature is carried to the boiling point thedyestufi no I produced dissolves in concentrated sulphuric parts ofthionyl chloride. The whole is 1 acid to a blue solution and dyes woolin stirred for some time, filtered,'was hed, and the vatbrown-red.dried. There 15 thus obtained a dark pow der which dissolves in.concentrated sul- E'aamnple' 3-. phuric acid to a magenta red solutionanddyeing wool in a vat brown-yellow. 1

78 parts of 2:5-dianil1d0-6-methylbenzo- The following table exhibitsthe main quinone are suspended in 1000 parts of hiproperties of a numberof dyestuffs which trobenzene and mixed at 15 C. with 90 can be obtainedby the present'invent onz Sulphur A peataiice of Colour of theDiarylldoquinone halogen Solvent Temperature 1; edyestufl solution insulf compound powder phi i-icacid 2:5 para para dichloro-- dianllido-BmoLthlonyl- Nitrobenzene. Boiling. ljark brown. Reddish blue. Brown.

benzoqiilnone. chloride. 2Z511818-p818-dit0111ldld0-l)e11Z0qUlH0l18. Do;Do. Cold. Yellow-brown. Blue. Yellow-brown.2:5-ineta-meta-ditoluidido-benzoquin- Do. Do. Cold up to Yellow-brownRed-violet to Yellow-brown one. 120 C to red-brown. reddish-blue. tored-brown. 2:5-dimeta-xy1ldido-benzoquinonc. Do. Do. 100C. Dark olive.Greenish-grey. Grey-olive. 2:S-dipara-anisidido-bcnzoquinone. D0. D0.100 0. up to Red-brown to Pure blue to Brown-violet.

' boiling. brown-black. greenishblue.

2:5-dipara-phenetidido-benzoquinoiie. Do. Do. 100-120C I Dgrk red-Greenlsh blue. Violet-brown.

I l'OWD. 2:5-di(fl-naphthyl'amicld)-benzoquiii- Do. Do. C'old up to Darkbrown. Reddish-blue Brownto grey. one. 100C. todirtybliie.

. 2:5-dl01thO-Dltt311llldO-bBDZOqlllIIlODB. Do. Do. 100 0. up to Darkyellow, Red-brown, Red-brown, boiling. brown, dull yellow acidified tobrown-black. green. violetbi'own.

2:5-dimeta-nitranilido-benzoquiiione. Do. Do. Cold up to Yellow-brownBrown to yel- Brown.

- boiling. go dark low-olive.

IOWD. 2:5-dl-para-oxyanilido-benzoquinone. Do. Do. Do. Reddlsh- B1ue.-Yellow-brown, i brown to olive to grey.

black.

What I claim is: l and black powders, dissolving in concen- 1. As a newprocess,'the manufactureof trated sulphuric acid to brown to red and vatdyestuffs, which consists in causing blue solutions and giving withhydrosulphite thionyl-chloride to act upon 2: 5-diarylidoand causticsoda lye bright yellow to brown benzoquinones. v I vats from which woolis dyed fast yellow to 2. As a new process, the manufacture of brown,olive, and grey tints. vat dyestuffs, -Wh1Cl1 consists in causing 7. .Asnew products, the d estuffs obtained thionyl-chloride to act upon 2:5-d1arylidofrom 2: 5-dianil1dobenzoquinone and thiobenzoquinones inpresence'ofa diluent. nyl-chloride containing sulphur and also 3. As anew process, the manufacture of ,chlorine, which form'yellow to darkbrown vat dyestuffs, which consists n causing and black powders,dissolving in concen- -th1onyl-'chloride to act upon 2:5-d1an1l1d0-trated sulphuric acid to brown to red and benzoquinone. I 1 bluesolutions and giving with hyrdosulphite 4. As-a new process, themanufacture of and caustic soda lye bright yellow to brown vatdyestuffs, which consists in causing vats from which wool is dyed fastyellow to thionyl-chloride to act upon 2:5-d1an1lidobrown, ol ve, andgrey tints. benzoquinone in presence of a diluent. 8. Material dyed withthe dyestufi's of 5. As new products, the dyestuffs obtained claim 5.fIOIll'225-d1211Yl1ClObQ11ZOQll11101188 and thio- 9. Material dyed withthe dyestuffs of nyl-cliloridc, which form yellow to dark claim 6. r Ibrown and black powders, dissolving in con- 10. Material dyed with thedyestuffs of centrated sulphuric acid t9 brown to red claim 7.

and blue solutions and giving with hydrosulphite and caustic soda lyebright yellow to brown vats from which wool is dyed fast yellow tobrown, olive and grey tints.

6. As new products, the dyestuffs obtained from 2:5-diarylidobenzoquinones and thionyl-chloride containing sulphur andalso chlorine, which form yellow to dark brown In witness whereof I havehereunto signed my name this 16th day of October 1924, in the presenceof two subscribing witnesses.

JAROSLAV FRUHLICH. Witnesses AMANI) BRAUN, JAS. RIEK, Jun.

